The remarkable luminescence properties of the platinum(II) complex 1,3-di(2-pyridyl)benzene, acting as a terdentate N=C=N-coordinating ligand cyclometalated at C2 benzene ring ([PtL(1)Cl]), have been investigated, together with those two new 5-substituted analogues [PtL(2)Cl] and [PtL(3)Cl] [HL(2) = methyl-3,5-di(2-pyridyl)benzoate; HL(3) 3,5-di(2-pyridyl)toluene]. All three complexes are intense emitters in degassed solution 298 K (lambda(max) 480-580 nm; phi(lum) 0.60, 0.58, 0.68...

We report attempts to prepare uranyl(VI)- and uranium(VI) carbenes utilizing deprotonation oxidation strategies. Treatment of the uranyl(VI)-methanide complex [(BIPMH)UO(2)Cl(THF)] [1, BIPMH = HC(PPh(2)NSiMe(3))(2)] with benzyl-sodium did not afford a uranyl(VI)-carbene via deprotonation. Instead, one-electron reduction isolation di- trinuclear [UO(2)(BIPMH)(μ-Cl)UO(μ-O){BIPMH}] (2) [UO(μ-O)(BIPMH)(μ(3)-Cl){UO(μ-O)(BIPMH)}(2)] (3), respectively, concomitant elimination dibenzyl, was...

A straightforward oxidation strategy affords the first pentavalent uranium carbene complex, 2. Owing to structural similarity of 1 and 2, it was possible for time directly probe differences in UC bonding on UIV UV.

The hysteresis of magnetization the anionic, neutral, and cationic forms a bis(phthalocyaninato)terbium-based complex ([Pc2Tb]−/0/+) have been determined using magnetic circular dichroism (MCD) spectroscopy in frozen dilute solutions at low temperatures (1.5 K) showing that three oxidation states exhibit single-molecule behaviors.

Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, data storage devices. The increasing miniaturization of device architectures produces need to develop analytical tools capable precisely probing spin information at the single-particle level. In this work, we demonstrate methodology using negatively charged nitrogen vacancies (NV–) fluorescent nanodiamond (FND) particles probe magnetic...

A new N,O-bidentate pro-ligand (HL), [ML2] (M = Cu, Zn) and [CuL2][BF4] have been synthesised; [CuL2].4DMF [CuL2][BF4].2CH2Cl2 crystallographically spectroscopically characterised; these data indicate that [CuL2]+ cations are constituted as [Cu2+(L.)(L-)]+ involve the phenoxyl radical L..

A new N,O-bidentate, phenol–imidazole pro-ligand 2′-(4′,6′-di-tert-butylhydroxyphenyl)-4,5-diphenyl imidazole (LH) has been designed, synthesised, and characterised. LH possesses no readily oxidisable position (other than the phenol) involves o- p-substituents on phenol ring that prevent radical coupling reactions. undergoes a reversible one-electron oxidation to generate corresponding [LH]˙+ cation phenoxyl character. The unusual reversibility of [LH]/[LH]˙+ redox couple is attributed, at...

A general route for synthesis of six structurally similar Pt(II) diimine thiolate/phenolates chromophores possessing bulky phenolate or thiolate ligands is reported. The Pt were characterized using an array techniques including 1H, 13C, and 195Pt NMR, absorption, emission, (spectro)electrochemistry, EPR spectroscopy. Systematic variation the electronic structure studied was achieved by (i) changing solvent polarity; (ii) substituting oxygen sulfur in donor ligand; (iii) alternating from bis-...

A series of mononuclear complexes the type [Pt(Bu2cat)(4,4′-R2-bipy)] [where Bu2cat is dianion 3,5-tBu2-catechol and R = H, tBu, or C(O)NEt2] analogous dinuclear based on "back-to-back" bis-catechol ligand 3,3′,4,4′-tetrahydroxybiphenyl have been studied in detail both their ground excited states by a range physical methods including electrochemistry, UV/vis/near-IR, IR, electron paramagnetic resonance spectroelectrochemistry, time-resolved IR (TRIR) transient absorption (TA) spectroscopy....

Carbon monoxide is a key C1 feedstock for the industrial production of hydrocarbons, where it used to make millions tonnes chemicals, fuels, and solvents per annum. Many transition metal complexes can coordinate CO, but formation new C-C bonds in well-defined compounds from scission subsequent coupling two or more CO moieties at centre remains challenge. Herein, we report use low-coordinate iron(II) selective homologation affording unusual squaraines iron carboxylates ambient temperature...

Boron nitride nanotubes (BNNTs) are an emerging class of molecular container offering new functionalities and possibilities for studying molecules at the nanoscale. Herein, BNNTs demonstrated as highly effective nanocontainers polyoxometalate (POM) molecules. The encapsulation POMs within occurs spontaneously room temperature from aqueous solution, leading to self-assembly a POM@BNNT host–guest system. Analysis interactions between host-nanotube guest-molecule indicate that Lewis acid–base...

A combination of picosecond time-resolved infrared spectroscopy, transient absorption and nanosecond flash photolysis was used to elucidate the nature dynamics a manifold lowest excited states in Pt(phen-NDI)Cl2 (1), where NDI = strongly electron accepting 1,4,5,8-naphthalene-diimide group. 1 is first example PtII-diimine-diimide dyad. UV/vis/IR spectroelectrochemistry EPR studies electrochemically generated anions confirmed that unoccupied molecular orbital (LUMO) this system localized on...

A series of photosensitizers for NiO-based dye-sensitized solar cells is presented. Three model compounds containing a triphenylamine donor appended to boron dipyrromethene (bodipy) chromophore have been successfully prepared and characterised using emission spectroscopy, electrochemistry spectroelectrochemistry, ultimately direct the design dyes with more complex structures. Carboxylic acid anchoring groups thiophene spacers were provide five which adsorbed onto NiO integrated into cells....

A synthetic strategy is reported for a general route to asymmetric dithiolenes. This has been used the generation of [MoO(dithiolene)2]2– complexes [dithiolene = –SC(H)CS–, R phenyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, quinoxalin-2-yl or 2-(dimethylaminomethyleneamino)-3-methyl-4-oxopteridin-6-yl], which have characterised by analysis, spectroscopy and electrochemistry. The prototypical compound [PPh4]2[MoO(sdt)2]·EtOH, where sdt α,β-styrenedithiolate (R phenyl), crystallises in space...

Two pro-ligands ((R)LH) comprised of an o,p-di-tert-butyl-substituted phenol covalently bonded to a benzimidazole ((Bz)LH) or 4,5-di-p-methoxyphenyl substituted imidazole ((PhOMe)LH), have been structurally characterised. Each possesses intramolecular O-H[dot dot dot]N hydrogen bond between the phenolic O-H group and nitrogen atom (1)H NMR studies show that this is retained in solution. (R)LH undergoes electrochemically reversible, one-electron, oxidation form [(R)LH] (+) radical cation...

The new phenol-imidazole pro-ligands (R)LH react with Co(BF(4))(2).6H(2)O in the presence of Et(3)N to form corresponding [Co(II)((R)L)(2)] compound (R = Ph (1), PhOMe (2), or Bz (3)). Also, (Bz)LH, reacts Co(ii) and H(2)O(2) [Co(III)((Bz)L)(3)](4). structures 1.2.5MeCN, 2.2DMF, 3.4MeOH, 4.4DMF have been determined by X-ray crystallography. 1, 2, 3 each involve Co(II) bound two N,O-bidentate ligands a distorted tetrahedral coordination sphere; 4 involves Co(III) three mer-N(3)O(3) octahedral...

The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)3(dppz-X2)], (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; X CH3, H, F, Cl, CF3) are reported. For all complexes the calculations show that lowest unoccupied molecular orbital (LUMO) is a phenazine based localized on dppz ligand. We observe three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), MLCT...

Stack them up! AgI ions combined with functionalized fullerenes (C60) form either discrete binuclear metallacycles or extended polymeric networks (see structure), depending on the geometry of functional groups fullerene and conditions assembly, such as choice solvent. Supporting information for this article is available WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700769_s.pdf from author. Please note: The publisher not responsible content functionality any supporting supplied by...

A series of catechols with attached imide functionality (imide = phthalimide PHT, 1,8-naphthalimide NAP, 1,4,5,8-naphthalenediimide NDI, and NAP-NDI) has been synthesized coordinated to the Pt (II)(bpy*) moiety, yielding Pt(bpy*)(cat-imide) complexes (bpy* 4,4'-di- tert-butyl-2,2'-bipyridine). X-ray crystal structures PHT NAP show a distorted square-planar arrangement ligands around center. Both form "head-to-tail" dimers in solid state through remarkably short unsupported Pt...Pt contacts...

Eine einfache Oxidationsstrategie lieferte den ersten Carbenkomplex von fünfwertigem Uran (2). Dank der ähnlichen Strukturen 1 und 2 konnten auch erstmals die Unterschiede im Doppelbindungsverhalten bei Oxidation UIV zu UV untersucht werden. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: The publisher is responsible for...

Five-coordinate Zn(II), Ni(II), and Cu(II) complexes containing pentadentate N(3)O(2) Schiff base ligands [1A](2-) [1B](2-) have been synthesized characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, phenolate O-donors, a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic suggest that the coordination spheres of [Cu(1A)] [Cu(1B)] are retained CH(2)Cl(2) solution solid-state...

The redox processes associated with BODIPY analogues are studied by electrochemical and spectroscopic methods revealing a characteristic profile for the persistent radical quenching of fluorescence upon reduction.

A linear asymmetric Pt(ii) trans-acetylide donor-bridge-acceptor triad designed for efficient charge separation, NAP[triple bond, length as m-dash]Pt(PBu3)2[triple m-dash]Ph-CH2-PTZ (), containing strong electron acceptor and donor groups, 4-ethynyl-N-octyl-1,8-naphthalimide (NAP) phenothiazine (PTZ) respectively, has been synthesised its photoinduced transfer processes characterised in detail. Excitation with 400 nm, ∼50 fs laser pulse initially populates a manifold stemming from the...

F64Pc2Ln (1Ln, Ln = Tb or Lu) represent the first halogenated phthalocyanine double-decker lanthanide complexes, and 1Tb exhibits single-molecule magnet properties as revealed by solid-state magnetometry. The fluorine substituents of rings have a dramatic effect on redox namely, stabilization their reduced states. Electrochemical spectroelectrochemical measurements demonstrate that 1Tb–/2– 1Tb2–/3– couples exhibit reversibility 1Tb–, 1Tb2– 1Tb3– species may be prepared bulk electrolysis in...

A strategy for positioning, and loosely connecting, molecules in close proximity using mechanically interlocked handcuffs is described. The demonstrated rylene diimides, creating dimeric structures which two components are linked through pillar[5]arene/imidazolium rotaxanes. Investigation of the resulting demonstrates intriguing new properties that arise from placing these redox active dye together, allowing interactions, whilst to separate as required. In particular we observe excimer...